JPS5825692B2 - Setup polyolefin inserts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyolefin composition with excellent adhesive properties.

Various efforts have been made in the past to improve the lack of adhesiveness, which is a drawback of polyolefins, and from this perspective, the present inventors have also made the following efforts, as shown in Japanese Patent Application No. 48-47588.
We are proposing a method for synthesizing modified polyethylene with excellent adhesive properties modified with maleic acids.

The method disclosed in Japanese Patent Publication No. 42-6178 is also of the same type.

However, when manufacturing a laminate by melt-bonding an olefin copolymer modified with unsaturated carboxylic acids or their anhydrides with metal, etc., it is necessary to prevent oxidative deterioration of the polyolefin during melting and to stabilize the weather resistance of the polyolefin after bonding. For reasons such as maintaining the properties of the olefin copolymer, so-called oxidation-resistant and weather-resistant stabilizers are often added, but these stabilizers ooze out to the interface between the olefin copolymer and the adherend, causing The effect of modifying polyolefin with unsaturated carboxylic acid or its acid anhydride is reduced.

The present inventors conducted intensive studies to overcome this drawback, and as a result, they arrived at the present invention.

The present invention is directed to an olefin polymer (A) having the general formula (zl
and z2 are an alkylene group, an arylene group, a cycloalkylene group, or a group consisting of a bond thereof, and may be the same or different from each other. represents a group consisting of a bond.

However, R1 and R2 may be the same or different, but at least one of them is an organic group.

m and n are O or 1, and may be the same or different from each other) A copolymer CB of a monomer [I] and an olefin] and an unsaturated carboxylic acid or an acid anhydride thereof A composition consisting of a copolymer [C] containing a polymer and an olefin, and the phenol units constituting the copolymer [B] are 10-7 m per 1 g of the composition.
The present invention relates to a highly adhesive composition characterized in that it is blended so that the adhesiveness is 01 or more.

Examples of the olefin polymer used in the present invention include high-density polyethylene, medium-density polyethylene, low-density polyethylene, and ethylene-vinyl acetate copolymer (ethylene content: 60
mol% or more), polypropylene, ethylene-propylene copolymer, poly-1-butene, ethylene-1-butene copolymer, poly-4-methyl-1-pentene, and compositions thereof.

In the present invention, the copolymer used as the acid component [B] usually has a viscosity average molecular weight of 1000 or more, preferably 500
0 or more, and the monomer unit content represented by general formula [I] in the copolymer is usually 0.001 to 20
% by mole, preferably from 0.01 to 10 mol%.

Its synthesis can be carried out, for example, by copolymerization of an olefin and the monomers listed below, or by copolymerizing an olefin with an unsaturated alcohol or its ester moiety constituting the monomer represented by the general formula. After copolymerizing, the hydroxyl group or the hydroxyl group generated by hydrolysis of the ester is esterified by a polymer reaction using a carboxylic acid corresponding to the monomer nocarboxylic acid moiety represented by the general formula [I]. It can be achieved.

Of course, other known methods for synthesizing the [B] acid component may also be used.

This component may contain unreacted hydroxyl groups and/or ester bonds.

The monomer that is the raw material for the component CB in the composition of the present invention is a monomer represented by the following general formula [I].

(In this 5, Zl and z2 are usually an alkylene group containing 1 to 10 carbon atoms, an arylene group, a cycloalkylene group, or a group consisting of a bond thereof, R1 and R2
is hydrogen, an alkyl group usually containing 1 to 8 carbon atoms, an aryl group usually containing 6 to 12 carbon atoms, a cycloalkyl group usually containing 3 to 6 carbon atoms, or a group consisting of a bond thereof. It is.

However, R1 and R2 may be the same or different, and at least one of them is an organic group.

) One method for synthesizing the monomer [1) used in the method ('i) above is a method in which the missing unsaturated alcohol and an aromatic carboxylic acid are reacted by a conventional method to esterify it. I can do it.

Examples of unsaturated alcohols used in this step 5 include the following.

Vinyl alcohol, allyl alcohol, 3-butene-
1-ol, 4-penten-1-ol, 5-hexen-1-ol, 6-hebuten-1-ol, 7-octen-1-ol, 10-undecen-1-ol, 2
-Methyl-3-buten-1-ol, 5-hexene-2
-ol, 2-allylic alcohol, 4-7" tenylphenol, 2-phenyl-4-penten-ol, 4-
Vinylphenol, 4-vinylcyclohexanol.

Moreover, the following can be illustrated as an aromatic carboxylic acid.

3-Methyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3゜5-dimethyl-
4-Hydroxybenzoic acid, 3-tert-butyl-4-hydroxy-benzoic acid, 3-tert-butyl-5-methyl-4-hydroxybenzoic acid, 3-tert-butyl-6-methyl-4-
Hydroxybenzoic acid, 3-tert-butyl-5-ethyl-4
-Hydroxybenzoic acid, 3-tert-butyl-6-ethyl-
4-Hydroxybenzoic acid, 3-tert-octyl-4-hydroxybenzoic acid, 3-tert-octyl-5-methyl-4-
Hydroxybenzoic acid, 3-tertiary octyl-6-methyl-
4-hydroxybenzoic acid, 2-(3-methyl-4-hydroxyphenyl)acetic acid, 2-(3,5-dimethyl-4-
hydroxyphenyl)acetic acid, 2-(3,5-ditert-butyl-4-hydroxyphenyl)acetic acid, 2-(3-tert-butyl-4-hydroxyphenyl)acetic acid, 2-(3-tert-butyl-5-methyl- 4-hydroxyphenyl)acetic acid,
2-(3-tert-butyl-6-methyl-4-hydroxyphenyl)acetic acid, 2-(3-tert-phthyl-5-ethyl-4
-Hydroxyphenyl)acetic acid, 2-(3-tert-butyl-
6-ethyl-4-hydroxyphenyl)acetic acid, 2-(3
-tertiary octyl-4-hydroxyphenyl)acetic acid, 2-
(3-tertiary octyl-5-methyl-4-hydroxyphenyl)acetic acid, 2-(3-tertiary octyl-6-methyl-4-hydroxyphenyl)acetic acid, 3-(3-methyl-4
-hydroxyphenyl)furopionic acid, 3-(3,5-
dimethyl-4-hydroxyphenyl)propionic acid, 3
-(3,5-di-tert-butyl-4-hydroxyphenyl)
Propion e, 3 (3-tert-butyl-4-hydroxyphenyl)propionic acid, 3-(3,5-di-tert-butyl-4-and mushy diphenyl)propionic acid, 3-(3-tert-butyl-4-hydroxyphenyl)propionic acid,
-tert-butyl-4-hydroxyphenyl)propionic acid, 3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionic acid, 3-(3-i tert-butyl-6-
Methyl-4-hydroxyphenyl)propionic acid, 3-
(3-tert-butyl-5-ethyl-4-hydroxyphenyl)propionic acid, 3-(3-tert-butyl-6-ethyl-4-hydroxyphenyl)propionic acid, 3-(3-
tert-octyl-4-hydroxyphenyl)propionic acid, 3-(3-Igtrioctyl-5-methyl-4-hydroxyphenyl)propionic acid, 3-(3-tert-octyl-6-methyl-4-hydroxyphenyl) Propionic acid, 3-(3,5-didodecyl-4-hydroxyphenyl)propionic acid, 4 (3-methyl-4-hydroxyphenyl)butyric acid, 4-(3,5-dimethyl-4-hydroxyphenyl)butyric acid, 4 -(3,5-di-tert-butyl-4
-Hydroxyphenyl)butyric acid, 4-(3-tert-butyl-
4-hydroxyphenyl)butyric acid, 4-(3-tert-butyl-5-methyl-4-hydroxyphenyl)butyric acid, 4-(
3-tert-butyl-5-ethyl-4-hydroxyphenyl)butyric acid, 4-(3-tert-butyl-6-methyl-4-(5
-tert-butyl-6-ethyl-4-hydroxyphenyl)
Butyric acid, 4-(3-tert-octyl-5-methyl-4-hydroxyphenyl)butyric acid, 4-(3-tert-octyl-6-
Methyl-4-hydroxyphenyl)butyric acid.

Of course, the method for synthesizing the monomer represented by general formula [I] is not limited to the above-mentioned example, and various known methods can be used.

General formula [I] in component [B] constituting the composition of the present invention
The content of the component corresponding to the monomer represented by [B]
10-'mo1 or more per gram of component, preferably 5X10
”-' or 5X10-3mof.

Moreover, in the present invention, in addition to the content of the unit corresponding to [1] in component [B) falling within the above range, the content of the unit in the entire composition is within a specific range. It is necessary.

That is, the composition should be prepared such that the phenol units in the constituent units of copolymer CB) are 10-7 mol or more per 1 g of the composition.

The copolymer (C) used in the present invention can be produced by known methods, such as radical copolymerization of an olefin and an unsaturated carboxylic acid or an acid anhydride thereof, or a monopolymer or a copolymer of an olefin with an unsaturated carboxylic acid or an acid thereof. It can be produced by means such as graft copolymerization of anhydrides.

Unsaturated carboxylic acids or their acid anhydrides which are raw materials constituting the copolymer [C] include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid,
Mezaconic acid, 5-norbornene-2,3-dicarboxylic acid, alkyl-5-norbornene-2,3-dicarboxylic acid, acrylic anhydride, methacrylic anhydride, itaconic anhydride, maleic anhydride, citracone acid anhydride, 5
Examples include -norbornene-2,3-dicarboxylic anhydride and alkyl-5-norbornene-2,3-dicarboxylic anhydride, with maleic acid, fumaric acid, and maleic anhydride being particularly preferred.

The content of the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride unit constituting the copolymer [C] in the copolymer [C] is preferably 1X10-' mol or more per 1 g of the copolymer [C]. The amount is selected to be 3×10 −′ moles or more.

Moreover, in the present invention, in addition to the content of the unsaturated carboxylic acid or acid anhydride unit of the unsaturated carboxylic acid in the component [C] being within the above range, the content of the unit in the entire composition is must be within a certain range.

That is, the composition should be prepared such that the content of the carboxylic acid or acid anhydride units constituting [C] is 10 -7 mol or more per 1 g of the composition.

In such a composition, the stable core unit is fixed in the copolymer CB), and the stabilizer does not ooze out to the interface of the laminate between the resin and the metal. The adhesion effect of the carboxylic acid or acid anhydride group contained in is not impaired.

Therefore, it can be bonded to metals, glass, ceramics, etc. extremely well, and it is also extremely durable.The method of using the composition of the present invention is to continuously extrude the composition under heating using an extruder. The composition may be melt-adhered to iron plates, steel pipes, aluminum plates, etc., or the composition may be applied in powder form to the surface of workpieces made of iron, aluminum, glass, ceramics, etc. by fluidized dipping, electrostatic coating, etc. It can also be coated.

Example 1 80A? Kerosene 327 was put into a stainless steel polymerization vessel, and after the atmosphere was sufficiently purged with nitrogen, 24 moles of diethylaluminium chloride was charged.

Next, from the dropping funnel, lO-undecen-1-ol 24
mol was added dropwise over 1 hour, and the mixture was reacted at 70°C for 30 minutes.

Furthermore, 160 g of titanium trichloride (AA grade, manufactured by Nutofer Chemical Co., Ltd.) was added, the temperature was raised to 85° C., and then polymerization was carried out for 3 hours while introducing propylene.

After the polymerization was completed, the catalyst was decomposed with a large excess of methanol, and the polymer was washed repeatedly and dried under reduced pressure at 70°C overnight.

As a result, 1 copolymer with propylene containing 0.84 mmol of 10-undecen-1-ol per 1 g of copolymer.
5.2 KP was obtained.

Next, 800 g of purified Xylene 4811 copolymer and 3-(3', 5'
-Ethyl di-tert-butyl-4'-hydroxyphenyl)propionate IK? , charged with 10 g of concentrated sulfuric acid, and heated with stirring for 3 hours.
The mixture was heated to reflux for an hour.

Xylene 32A' was removed from this product solution by atmospheric distillation, and after the system was cooled to room temperature, acetone was introduced into the residue to precipitate the product in powder form.

After repeatedly washing the precipitate with acetone, it was dried under reduced pressure to obtain 785 g of a white powdery product.

According to infrared absorption analysis, the content of phenol structure, which is a stable nuclear unit, per 1 g was 0.63 millicells.

0.3 parts by weight of this stable core-containing propylene copolymer and 2.0×10 maleic anhydride units per 1 g of the copolymer.
- Maleic anhydride grafted polyethylene containing 4 moles 1
．． 0 parts by weight of polyethylene (HIZEX ■2100L
P, manufactured by Mitsui Petrochemical Industries, Ltd.) 98.7 parts by weight,
Melt and knead at 200°C in an extruder to a thickness of about 2y.
Extruded into a sheet with a thickness of 0 nm and preheated on both sides.
．． Two mirror-finished aluminum plates (with the oil and fat deposited on the surface removed) were pressed together, and the surface cooling rate was set to 80'C/
A laminate having a thickness of 2 mvt was obtained by cooling to around room temperature while regulating the temperature at a rate of 18° C./min to 18° C./min.

This laminate was divided into three parts, the aluminum plate on the surface of one part was raised by a width of 11 nch, and the adhesive strength with the polyethylene layer was measured by a peel test.
A laminate of 72
Table 1 shows the results of the time accelerated deterioration test.

From the table, the composition of the present invention (experiment number 3) is excellent in both initial adhesive strength and adhesive strength after the deterioration test.
Furthermore, it can be seen that the decrease in adhesive strength due to deterioration is slight.

Example 2 40 liters of benzene and 10 liters of benzene were placed in a 2001 stainless steel reactor.
% sodium hydroxide aqueous solution 407% and a commercially available ethylene-vinyl acetate copolymer (vinyl acetate content per 1 g of copolymer: 3.84 mmoi!) 2 KP were charged, heated under reflux for 3 hours, and then distilled by steam distillation. 4.3 mmol per 1g of copolymer! An ethylene/vinyl alcohol copolymer containing 1.32 KP of hydroxyl groups was obtained.

Purified xylene 6011 in 2001 stainless steel reactor
Ethylene-vinyl alcohol copolymer 2 obtained above
00 g of ethyl 3-(3,5-ditertiarybutyl-4-hydroxyphenyl)propionate, 1.32 Kp, and 40 g of para-toluenesulfonic acid were charged and heated under reflux for 6 hours.

When a large excess of acetone was added to precipitate the product, a slightly yellowish white powder product was obtained.
g was obtained.

As a result of infrared absorption analysis, this product has a stable nuclear unit of 1.8
It was an ethylene-vinyl alcohol copolymer containing mmo7/g.

1 part by weight of this stable core-containing ethylene copolymer and 5 parts by weight of acrylic acid grafted polypropylene containing 1.0 x 10-3 mol of acrylic acid units in 1 g were mixed with polypropylene (Mitsui Petrochemical Polypropylene oF600, Mitsui Petrochemical Industries (Ha)). A composition containing 94 parts by weight (manufactured by) was used, and a thickness of approximately 100 μm was formed using a blown film molding method.
obtained the film.

This film was kept on an iron plate (10
0iiX 30iiX 5mm) and then rapidly cooled.

The polypropylene layer was peeled off, and the adhesive strength between the polypropylene layer and the iron plate was measured.

The results are shown in Table 2.

It can be seen from the table that the composition of the present invention (Experiment No. 4) exhibits twice as much adhesive strength as the composition containing a conventional stabilizer.

Claims (1)

[Claims] 1. Olefin polymer prisoner, general formula (where Zl and z2 are alkylene groups, A IJ ''+
R1 and R2 represent hydrogen, an alkyl group, an aryl group, a cycloalkyl group, or a group consisting of a bond thereof, which may be the same or different from each other. . However, R1 and R2 may be the same or different, but at least one of them is an organic group. m and n are O or 1 and may be the same or different from each other) and a copolymer of an olefin (CB) and a monomer selected from an unsaturated carboxylic acid or an acid anhydride thereof. A composition consisting of a copolymer [C] containing a copolymer [B] and a phenol unit containing 1 g of the composition, and 10 phenol units constituting the copolymer [B]
A polyolefin composition characterized in that it is blended so that mo1 or more is 7.